Dishwashing method

ABSTRACT

A method of washing dishware/tableware in an automatic dishwashing machine, the method comprising simultaneously or sequentially delivering quantities of a particulate or densified particulate automatic dishwashing product and of an anhydrous liquid, gel or paste form dishwashing detergent auxiliary contained in separate compartments of a multi-compartment pouch into the same or different cycles of the dishwashing machine. The method provides improved cleaning performance and product stability.

TECHNICAL FIELD

The present invention is in the field of dishwashing, in particular itrelates to dishwashing methods including methods for washingdishware/tableware in an automatic dishwashing machine using dishwashingproducts in multi-compartment pouch form. The methods of the inventionprovide excellent cleaning results.

BACKGROUND OF THE INVENTION

Unitised doses of dishwashing detergents are found to be more attractiveand convenient to some consumers because they avoid the need of theconsumer to measure the product thereby giving rise to a more precisedosing and avoiding wasteful overdosing or underdosing. For this reasonautomatic dishwashing detergent products in tablet form have become verypopular. Detergent products in pouch form are also known in the art.

It is well known to use bleach in dishwashing detergent formulations inorder to remove stains, especially tea, coffee, fruit juice andcarotenoid stains. Chlorine and peroxygen bleaches are effective forstain removal. While chlorine bleach is a very effective cleaning agent,it is not compatible with a variety of detergent ingredients and mayrequire additional processing in order to be incorporated into a finalproduct. Peroxide bleaches on the other hand are more compatible withconventional detergent ingredients. However, one of the problems foundwhen formulating peroxygen containing dishwashing detergent compositionsis the fact that the bleach is liable to decompose in contact withmoisture, thereby reducing the amount of active bleach available for thedishwashing process. Once the decomposition process is initiated,moreover, decomposition is auto catalysed by the presence of freeradicals generated by the decomposition process. The products of bleachdecomposition can also oxidise detergency enzymes, thereby reducing theamount of enzyme available for the dishwashing process.

In the case of flexible unitised doses such as pouches, capsules orsachets which are moisture permeable, bleach decomposition gives rise toan additional problem due to the generation of gaseous oxygen. Usuallythe pouch material is not permeable to oxygen and this can lead tobloating or even destruction of the pouch and to a detrimental effect onappearance and on dispenser fit.

Some detergent ingredients used in dishwashing detergent compositionsare liquids. These liquid ingredients can be difficult or costly toinclude in a solid detergent composition. Also, certain ingredients arepreferably transported and supplied to detergent manufacturers in aliquid form and require additional, and sometimes costly, process stepsto enable them to be included in a solid detergent composition. Anexample of these detergent ingredients are surfactants, especiallynonionic surfactants which are typically liquid at room temperature orare typically transported and supplied to detergent manufacturers inliquid form. Another example are organic solvents.

Current methods of incorporating liquid ingredients into solid detergentcompositions include absorbing the liquid ingredient onto a solidcarrier, for example by mixing, agglomeration or spray-on techniques.Typically, solid detergent compositions comprise only low amounts ofthese liquid detergent ingredients due to the difficulty and expense ofincorporating these liquid ingredients into a solid detergent. Theproblems are particularly acute in the case of solid compositions whichare subject to a densification step and especially to the levels ofdensification applied in machine dishwashing tablet manufacture.Furthermore, the incorporation of liquid ingredients into soliddetergent compositions can impact on the dissolution characteristics ofthe composition (for example as the result of forming surfactant gelphases) and can also lead to problems of flowability. It would beadvantageous to have a detergent composition which allows the differentingredients to be in their natural state i.e., liquid or solid. Thiswould facilitate the manufacturing process and furthermore allow thedelivery of liquid ingredients prior or post to the delivery of solidingredients. For example differential dissolution of active ingredientswould be beneficial in the case of enzyme/bleach compositions to avoidoxidation of enzymes by the bleach in the dishwashing liquor. It wouldalso be advantageous to separate bleach from perfume.

An objective of the present invention is to provide dishwashing methodsand products delivering improved cleaning performance and productstability. Another object is to provide dishwashing methods and productswhich have simplified processing, which allow for the problems ofproduct incompatibility and which are capable of providing differentialdissolution of active components.

SUMMARY OF THE INVENTION

According to a first aspect of the present invention, there is provideda method of washing dishware/tableware in an automatic dishwashingmachine, the method comprising simultaneously or sequentially deliveringquantities of a particulate or densified particulate automaticdishwashing product and of an anhydrous liquid, gel or paste formdishwashing detergent auxiliary contained in separate compartments of amulti-compartment pouch into the same or different cycles of thedishwashing machine.

Suitable multi-compartment pouches (which term includes capsules,sachets and other compartmentalized unit dose containers) for use hereininclude water-soluble, water-dispersible and water-permeable pouches.Preferred for use herein are water soluble pouches, based on partiallyhydrolysed polyvinylacetate/polyvinyl alcohol as pouch material.Although, soluble in water, these pouches have the disadvantage thatthey are permeable to moisture.

The term anhydrous as used herein is intended to include compositionscontaining less than about 10% of water by weight of the composition,preferably less than about 5% of water and more preferably less thanabout 1%. The water can be present in the form of hydrated compounds,i.e. bound water or in the form of moisture. It is preferred that thecomposition contains less than about 1%, preferably less than about 0.1%free moisture. Free moisture can be measured by extracting 2 g of theproduct into 50 ml of dry methanol at room temperature for 20 minutesand then analysis a 1 ml aliquot of the methanol by Karl Fischertitration. The term water-soluble as used to describe the pouch meansthat the pouch or a compartment thereof dissolves or disperses in waterto release some or all of the contents thereof at some temperature orrange of temperatures in the normal operating range of a dishwashingmachine (ambient to 70° C.). Under other temperatures or conditions ofuse, however, the pouch or compartment thereof may be insoluble inwater, remaining intact for extended periods greater than that of thenormal operating regime of the dishwashing machine.

In a preferred embodiment the particulate dishwashing product isdensified. Densification can be achieved by compaction, compression,tamping, tapping, stamping, vibrating, subjecting to inertial forces,etc, densification being preferably such as to provide a bulk densityincrease of at least about 10%, preferably at least about 20%, morepreferably at least about 30%. The final bulk density is preferably atleast about 0.6 g/cc, more preferably at least about 0.8 g/cc,especially at least about 1 g/cc, and more especially at least about 1.3g/cc.

In a preferred embodiment, the densified particulate dishwashing productis in the form of a tablet. Multi-compartment pouches comprising atablet and an anhydrous liquid, gel or paste present the knownadvantages of tablets, such as high product density, minimum storagevolume requirements and efficient packing, but they also allow for thesimultaneous or sequential release of a liquid, gel or paste inquantities which it would be impossible to achieve through normaltabletting techniques. A further advantage of said pouches is that theuser does not touch or come into direct contact with the tablet and theremainder of the automatic dishwashing composition.

From the manufacturing viewpoint, multi-compartment pouches comprising aparticulate automatic dishwashing product in the form of a tablet arevery convenient because the filling of pouches with particulate productcan be complex and prone to inaccuracies. It is often slow and likely toproduce dust, such that it can be very difficult to avoid dustdeposition on the pouch seal area. This can be detrimental to achievinga strong seal.

The tablet can be formed using any suitable method, but preferably bycompression, for example in a tablet press. Preferably, the tablet is acompressed shaped body prepared by mixing together the components of theautomatic dishwashing detergent followed by applying a compressionpressure of at least about 40 kg/ cm², preferably at least about 250kg/cm², more preferably at least about 350 kg/cm² (3.43 kN/cm²), evenmore preferably from about 400 to about 2000, and especially from about600 to about 1200 kg/cm² (compression pressure herein is the appliedforce divided by the cross-sectional area of the tablet in a planetransverse to the applied force—in effect, the transversecross-sectional area of the die of the rotary press). Such tablets beingpreferred herein from the viewpoint of providing optimum tabletintegrity and strength (measured for example by the Child Bite Strength[CBS] test) and product dissolution characteristics. The tabletspreferably have a CBS of at least about 6 kg, preferably greater thanabout 8 kg, more preferably greater than about 10 kg, especially greaterthan about 12 kg, and more especially greater than about 14 kg, CBSbeing measured per the US Consumer Product Safety Commission TestSpecification.

The tablet can take a variety of geometric shapes such as spheres,cubes, etc but preferably has a generally axially-symmetric form with agenerally round, square or rectangular cross-section.

The tablet can be prepared such that it comprises at least one mould inits surface. The mould or moulds can also vary in size and shape and intheir location, orientation and topology relative to the tablet. Forexample, the mould or moulds can be generally circular, square or ovalin cross-section; they can form an internally-closed cavity, depressionor recess in the surface of the tablet, or they can extend betweenunconnected regions of the tablet surface (for example axially-opposedfacing surfaces) to form one or more topological ‘holes’ in the tablet;and they can be axially or otherwise symmetrically-disposed relative tothe tablet or they can be asymmetrically disposed. Preferably, the mouldis preformed, for example being created using a specially designedtablet press wherein the surface of the punch that contacts thedetergent composition is shaped such that when it contacts and pressesthe detergent composition it presses a mould, or multiple moulds intothe detergent tablet. Preferably, the mould will have an inwardlyconcave or generally concave surface to provide improved housing andphysical storage of the liquid, gel or paste containing compartment.Alternatively, the mould can be created by compressing a preformed bodyof detergent composition disposed annularly around a central dye,thereby forming a shaped body having a mould in the form of a cavityextending axially between opposing surfaces of the body. Tablets withmoulds are very useful from the viewpoint of accommodating thecompartment comprising the anhydrous liquid, gel or paste dishwashingdetergent auxiliary of the present invention.

According to a preferred embodiment of the present invention, theparticulate dishwashing product comprises one or more moisture-sensitivedetergent actives and the detergent auxiliary comprises a humectant inlevels sufficient to act as a moisture sink for stabilising themoisture-sensitive detergent active. A detergent active is considered tobe moisture-sensitive when it can interact with moisture to decrease itsdetergency activity as for example detergency bleach. Particulatebleaches suitable for use herein include inorganic peroxides inclusiveof perborates and percarbonates, organic peracids inclusive of preformedmonoperoxy carboxylic acids, such as phthaloyl amido peroxy hexanoicacid and di-acyl peroxides. Preferred peroxides for use herein arepercarbonate and perborate bleach.

Humectant is a substance which can pick up or emit moisture to thesurroundings depending on the surrounding relative humidity. Whenformulated as part of the detergent auxiliary, the humectants usedherein are capable of acting as moisture sink for the powder layer. Thisstabilises the moisture-sensitive detergent active. The humectantsshould have a humidity equilibrium point such as to enable them to actas moisture sink but preferably they should take up less than about 10%,more preferably less than about 5% even more preferably less than about1% of water at a relative humidity of 50% or less, preferably atrelative humidity of 75% or less, and more preferably at relativehumidity of 90% or less under ambient conditions of temperature andpressure (20° C. and 1 atmosphere). Humectants suitable for use hereininclude non-aqueous hydrophilic organic solvents inclusive of glycolsand polyhydric alcohols, for example sorbitol, glycerol, dipropyleneglycol and mixtures thereof, and also various hygroscopic solidsinclusive of inorganic or organic salts such as silicates, phosphatesand citrates, as well as sugars, etc. Preferred for use herein arehumectants and humectant mixtures comprising glycols, more preferablypolyethylene glycols and especially mixtures of polyethylene glycols ofdifferent molecular weight. For example, mixtures of polyethylene glycolhaving a molecular weight of about 200 to about 1,200, more preferablyfrom about 200 to about 800 and polyethylene glycol having a molecularweight of about 2,000 to about 6,000 more preferably from about 2,600 toabout 4,000. In the mixtures of polyethylene glycol used herein the lowmolecular weight and the high molecular weight polyethylene glycol areusually in a weight ratio of at least 10:1 and preferably at least100:1.

In a preferred embodiment, the anhydrous detergent auxiliary compositioncomprises a detergency enzyme. The enzyme is preferably in liquid formand is delivered to the wash liquor substantially prior to theparticulate products, thereby minimizing or avoiding interaction withactives, such as bleach, which can have a deleterious effect on enzymestability and performance in the wash solution.

In preferred embodiments the dishwashing composition comprises anorganic solvent system. The organic solvent system can simply act as aliquid carrier, but in preferred compositions, the solvent can aidremoval of cooked-, baked- or burnt-on soil and thus has detergentfunctionality in its own right. The organic solvent system (comprising asingle solvent compound or a mixture of solvent compounds) preferablyhas a volatile organic content above 1 mm Hg and more preferably above0.1 mm Hg of less than about 50%, preferably less than about 20% andmore preferably less than about 10% by weight of the solvent system.Herein volatile organic content of the solvent system is defined as thecontent of organic components in the solvent system having a vaporpressure higher than the prescribed limit at 25° C. and atmosphericpressure.

The organic solvent system for use herein is preferably selected fromorganoamine solvents, inclusive of alkanolamines, alkylamines,alkyleneamines and mixtures thereof; alcoholic solvents inclusive ofaromatic, aliphatic (preferably C₄-C₁₀) and cycloaliphatic alcohols andmixtures thereof; glycols and glycol derivatives inclusive of C₂-C₃(poly)alkylene glycols, glycol ethers, glycol esters and mixturesthereof; and mixtures selected from organoamine solvents, alcoholicsolvents, glycols and glycol derivatives. In one preferred embodimentthe organic solvent comprises organoamine (especially alkanolamine)solvent and glycol ether solvent, preferably in a weight ratio of fromabout 3:1 to about 1:3, and wherein the glycol ether solvent is selectedfrom ethylene glycol monobutyl ether, diethylene glycol monobutyl ether,ethylene glycol monomethyl ether, ethylene glycol monoethyl ether,diethylene glycol monomethyl ether, diethylene glycol monoethyl ether,propylene glycol monobutyl ether, and mixtures thereof. Preferably, theglycol ether is a mixture of diethylene glycol monobutyl ether andpropylene glycol butyl ether, especially in a weight ratio of from about1:2 to about 2:1.

According to another embodiment of the invention the dishwashingauxiliary composition can take the form of a paste having a densitygreater than about 1100 Kg/m³, preferably greater than about 1300 Kg/m³.

Multi-compartment pouches suitable for use herein can includecompartments with different solubility profiles controlled by forexample pH, temperature or any other means. High temperaturewater-soluble pouches allow handling of the pouches at ambienttemperature with wet hands.

The multi-compartment pouches herein comprise at least one compartmentcontaining a powder or densified powder composition and at least onecontaining an anhydrous liquid, gel or paste. This powder compositioncomprises traditional solid materials used in dishwashing detergent,such as builders, alkalinity sources, together with moisture-sensitivedetergent active such as bleaches, etc. The liquid, gel or pastecompositions comprise traditional liquid materials used in dishwashingdetergents, such as non-ionic surfactants or the organic solventsdescribed hereinabove together with a humectant. Preferably thecompartment comprising the detergent auxiliary is placed above oradjacent the compartment comprising the moisture-sensitive detergentactive in order to help protect the moisture-sensitive detergent activeand to reduce the surface area of the pouch containing compartment whichis exposed to moisture.

DETAILED DESCRIPTION OF THE INVENTION

The present invention envisages the use of dishwashing detergent andauxiliary compositions in a multi-compartment pouch, whereby amoisture-sensitive detergent active and a humectant are contained inseparate compartments. The humectant is capable of acting as a moisturesink and acts to stabilize the moisture-sensitive detergent active.

Unitised dose forms specially useful for use herein are pouches. Thepouch herein is typically a closed structure which comprises two or morecompartments, made of materials described herein. Subject to theconstraints of dispenser fit, the pouch can be of any form, shape andmaterial which is suitable to hold the composition, e.g. withoutallowing the release of the composition from the pouch prior to contactof the pouch to water. The exact execution will depend on, for example,the type and amount of the composition in the pouch, the number ofcompartments in the pouch, the characteristics required from the pouchto hold, protect and deliver or release the composition and/orcomponents thereof.

The composition, or components thereof, are contained in the internalvolume space of the pouch, and are typically separated from the outsideenvironment by a barrier of water-soluble material. Typically, differentcomponents of the composition contained in different compartments of thepouch are separated from one another by a barrier of water-solublematerial.

In the case of multi-compartment pouches, the compartments may be of adifferent colour from each other, for example a first compartment may begreen or blue, and a second compartment may be white or yellow. Onecompartment of the pouch may be opaque or semi-opaque, and a secondcompartment of the pouch may be translucent, transparent, orsemi-transparent. The compartments of the pouch may be the same size,having the same internal volume, or may be different sizes havingdifferent internal volumes.

For reasons of deformability and dispenser fit under compression forces,pouches or pouch compartments containing a component which is liquidwill usually contain an air bubble having a volume of up to about 50%,preferably up to about 40%, more preferably up to about 30%, morepreferably up to about 20%, more preferably up to about 10% of thevolume space of said compartment.

The pouch is preferably made of a pouch material which is soluble ordispersible in water, and preferably has a water-solubility of at least50%, preferably at least 75% or even at least 95%, as measured by themethod set out hereafter using a glass-filter with a maximum pore sizeof 20 microns.

50 grams±0.1 gram of pouch material is added in a pre-weighed 400 mlbeaker and 245 ml±1 ml of distilled water at the appropriate temperatureis added. This is stirred vigorously on a heatable plate with a magneticstirrer set at 600 rpm, for 30 minutes. Then, the mixture is filteredthrough a folded qualitative sintered-glass filter with a pore size asdefined above (max. 20 micron). The water is dried off from thecollected filtrate by any conventional method, and the weight of theremaining material is determined (which is the dissolved or dispersedfraction). Then, the % solubility or dispersability at the specifiedtemperature can be calculated.

Preferred pouch materials are polymeric materials, preferably polymerswhich are formed into a film or sheet. The pouch material can, forexample, be obtained by casting, blow-moulding, extrusion or blowextrusion of the polymeric material, as known in the art.

Preferred polymers, copolymers or derivatives thereof suitable for useas pouch material are selected from polyvinyl alcohols, partiallyhydrolysed polyvinylacetates, polyvinyl pyrrolidone, polyalkyleneoxides, acrylamide, acrylic acid, cellulose, cellulose ethers, celluloseesters, cellulose amides, polyvinyl acetates, polycarboxylic acids andsalts, polyaminoacids or peptides, polyamides, polyacrylamide,copolymers of maleic/acrylic acids, polysaccharides including starch andgelatine, natural gums such as xanthum and carragum. More preferredpolymers are selected from polyacrylates and water-soluble acrylatecopolymers, methylcellulose, carboxymethylcellulose sodium, dextrin,ethylcellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose,hydroxybutyl methylcellulose, maltodextrin, polymethacrylates, and mostpreferably selected from polyvinyl alcohols, polyvinyl alcoholcopolymers, partially hydrolysed polyvinylacetates and hydroxypropylmethyl cellulose (HPMC), hydroxybutyl methylcellulose (HBMC), andcombinations thereof. Preferably, the level of polymer in the pouchmaterial, for example a PVA polymer, is at least 60%.

The polymer can have any weight average molecular weight, preferablyfrom about 1000 to 1,000,000, more preferably from about 10,000 to300,000 yet more preferably from about 20,000 to 150,000.

Mixtures of polymers can also be used as the pouch material. This can bebeneficial to control the mechanical and/or dissolution properties ofthe compartments or pouch, depending on the application thereof and therequired needs. Suitable mixtures include for example mixtures whereinone polymer has a higher water-solubility than another polymer, and/orone polymer has a higher mechanical strength than another polymer. Alsosuitable are mixtures of polymers having different weight averagemolecular weights, for example a mixture of PVA or a copolymer thereofof a weight average molecular weight of about 10,000-40,000, preferablyaround 20,000, and of PVA or copolymer thereof, with a weight averagemolecular weight of about 100,000 to 300,000, preferably around 150,000.

Also suitable herein are polymer blend compositions, for examplecomprising hydrolytically degradable and water-soluble polymer blendssuch as polylactide and polyvinyl alcohol, obtained by mixingpolylactide and polyvinyl alcohol, typically comprising about 1-35% byweight polylactide and about 65% to 99% by weight polyvinyl alcohol.

Preferred for use herein are polymers inclusive of polyvinylacetatewhich are from about 60% to about 98% hydrolysed, preferably about 80%to about 90% hydrolysed, to improve the dissolution characteristics ofthe material.

Most preferred pouch materials are PVA films known under the tradereference Monosol M8630, as sold by Chris-Craft Industrial Products ofGary, Ind., US, and PVA films of corresponding solubility anddeformability characteristics. Other films suitable for use hereininclude films known under the trade reference PT film or the K-series offilms supplied by Aicello, or VF-HP film supplied by Kuraray.

The pouch material herein can also comprise one or more additiveingredients. For example, it can be beneficial to add plasticisers, forexample glycerol, ethylene glycol, diethyleneglycol, propylene glycol,sorbitol and mixtures thereof. Other additives include functionaldetergent additives to be delivered to the wash water, for exampleorganic polymeric dispersants, etc.

The pouch can be prepared according to methods known in the art. Thepouch is typically prepared by first cutting an appropriately sizedpiece of pouch material, preferably the pouch material. The pouchmaterial is then folded to form the necessary number and size ofcompartments and the edges are sealed using any suitable technology, forexample heat sealing, wet sealing or pressure sealing. Preferably, asealing source is brought into contact with the pouch material, heat orpressure is applied and the pouch material is sealed.

The pouch material is typically introduced to a mould and a vacuumapplied so that the pouch material is flush with the inner surface ofthe mould, thus forming a vacuum formed indent or niche in said pouchmaterial. This is referred to as vacuum-forming.

Another suitable method is thermo-forming. Thermo-forming typicallyinvolves the step of forming an open pouch in a mould under applicationof heat, which allows the pouch material to take on the shape of themould.

Typically more than one piece of pouch material is used for makingmulti-compartment pouches. For example, a first piece of pouch materialcan be vacuum pulled into the mould so that said pouch material is flushwith the inner walls of the mould. A second piece of pouch material canthen be positioned such that it at least partially overlaps, andpreferably completely overlaps, with the first piece of pouch material.The first piece of pouch material and second piece of pouch material aresealed together. The first piece of pouch material and second piece ofpouch material can be made of the same type of material or can bedifferent types of material.

In a preferred process, a piece of pouch material is folded at leasttwice, or at least three pieces of pouch material are used, or at leasttwo pieces of pouch material are used wherein at least one piece ofpouch material is folded at least once. The third piece of pouchmaterial, or a folded piece of pouch material, creates a barrier layerthat, when the sachet is sealed, divides the internal volume of saidsachet into at least two or more compartments.

The pouch can also be prepared by fitting a first piece of the pouchmaterial into a mould, for example the first piece of film may be vacuumpulled into the mould so that said film is flush with the inner walls ofthe mould. A composition, or component thereof, is typically poured intothe mould. A pre-sealed compartment made of pouch material, is thentypically placed over the mould containing the composition, or componentthereof. The pre-sealed compartment preferably contains a composition,or component thereof. The pre-sealed compartment and said first piece ofpouch material may be sealed together to form the pouch.

The detergent auxiliary herein can comprise traditional detergencycomponents and can also comprise organic solvents having a cleaningfunction and organic solvents having a carrier or diluent function orsome other specialised function. The compositions will generally bebuilt and comprise one or more detergent active components which may beselected from colorants, bleaching agents, surfactants, alkalinitysources, enzymes, thickeners (in the case of liquid, paste, cream or gelcompositions), anti-corrosion agents (e.g. sodium silicate) anddisrupting and binding agents (in the case of powder, granules ortablets). Highly preferred detergent auxiliary components include abuilder compound, an alkalinity source, a surfactant, an enzyme and ableaching agent.

Unless otherwise specified, the components described hereinbelow can beincorporated either in the automatic dishwashing product or detergentauxiliary.

The organic solvents should be selected so as to be compatible with thetableware/cookware as well as with the different parts of an automaticdishwashing machine. Furthermore, the solvent system should be effectiveand safe to use having a volatile organic content above 1 mm Hg (andpreferably above 0.1 mm Hg) of less than about 50%, preferably less thanabout 30%, more preferably less than about 10% by weight of the solventsystem. Also they should have very mild pleasant odours. The individualorganic solvents used herein generally have a boiling point above about150° C., flash point above about 100° C. and vapor pressure below about1 mm Hg, preferably below 0.1 mm Hg at 25° C. and atmospheric pressure.

Solvents that can be used herein include: i) alcohols, such as benzylalcohol, 1,4-cyclohexanedimethanol, 2-ethyl-1-hexanol, furfuryl alcohol,1,2-hexanediol and other similar materials; ii) amines, such asalkanolamines (e.g. primary alkanolamines: monoethanolamine,monoisopropanolamine, diethylethanolamine, ethyl diethanolamine;secondary alkanolamines: diethanolamine, diisopropanolamine,2-(methylamino)ethanol; ternary alkanolamines: triethanolamine,triisopropanolamine); alkylamines (e.g. primary alkylamines:monomethylamine, monoethylamine, monopropylamine, monobutylamine,monopentylamine, cyclohexylamine), secondary alkylamines:(dimethylamine), alkylene amines (primary alkylene amines:ethylenediamine, propylenediamine) and other similar materials; iii)esters, such as ethyl lactate, methyl ester, ethyl acetoacetate,ethylene glycol monobutyl ether acetate, diethylene glycol monoethylether acetate, diethylene glycol monobutyl ether acetate and othersimilar materials; iv) glycol ethers, such as ethylene glycol monobutylether, diethylene glycol monobutyl ether, ethylene glycol monomethylether, ethylene glycol monoethyl ether, diethylene glycol monomethylether, diethylene glycol monoethyl ether, propylene glycol butyl etherand other similar materials; v) glycols, such as propylene glycol,diethylene glycol, hexylene glycol (2-methyl-2,4 pentanediol),triethylene glycol, composition and dipropylene glycol and other similarmaterials; and mixtures thereof.

Surfactant

In the methods of the present invention, the detergent surfactant ispreferably low foaming by itself or in combination with other components(i.e. suds suppressers). Surfactants suitable herein include anionicsurfactants such as alkyl sulfates, alkyl ether sulfates, alkyl benzenesulfonates, alkyl glyceryl sulfonates, alkyl and alkenyl sulphonates,alkyl ethoxy carboxylates, N-acyl sarcosinates, N-acyl taurates andalkyl succinates and sulfosuccinates, wherein the alkyl, alkenyl or acylmoiety is C₅-C₂₀ , preferably C₁₀-C₁₈ linear or branched; cationicsurfactants such as chlorine esters (U.S. Pat. No. 4,228,042, U.S. Pat.No. 4,239,660 and U.S. Pat. No. 4,260,529) and mono C₆-C₁₆ N-alkyl oralkenyl ammonium surfactants wherein the remaining N positions aresubstituted by methyl, hydroxyethyl or hydroxypropyl groups; low andhigh cloud point nonionic surfactants and mixtures thereof includingnonionic alkoxylated surfactants (especially ethoxylates derived fromC₆-C₁₈ primary alcohols), ethoxylated-propoxylated alcohols (e.g., OlinCorporation's Poly-Tergent® SLF18), epoxy-capped poly(oxyalkylated)alcohols (e.g., Olin Corporation's Poly-Tergent® SLF18B—seeWO-A-94/22800), ether-capped poly(oxyalkylated) alcohol surfactants, andblock polyoxyethylene-polyoxypropylene polymeric compounds such asPLURONIC®, REVERSED PLURONIC®, and TETRONIC® by the BASF-WyandotteCorp., Wyandotte, Mich.; amphoteric surfactants such as the C₁₂-C₂₀alkyl amine oxides (preferred amine oxides for use herein includelauryldimethyl amine oxide and hexadecyl dimethyl amine oxide), andalkyl amphocarboxylic surfactants such as Miranol™ C2M; and zwitterionicsurfactants such as the betaines and sultaines; and mixtures thereof.Surfactants suitable herein are disclosed, for example, in U.S. Pat. No.3,929,678, U.S. Pat. No. 4,259,217, EP-A-0414 549, WO-A-93/08876 andWO-A-93/08874. Surfactants are typically present at a level of fromabout 0.2% to about 30% by weight, more preferably from about 0.5% toabout 10% by weight, most preferably from about 1% to about 5% by weightof composition. Preferred surfactant for use herein are low foaming andinclude low cloud point nonionic surfactants and mixtures of higherfoaming surfactants with low cloud point nonionic surfactants which actas suds suppresser therefor.

Builder

Builders suitable for use in detergent and cleaning compositions hereininclude water-soluble builders such as citrates, carbonates andpolyphosphates e.g. sodium tripolyphosphate and sodium tripolyphosphatehexahydrate, potassium tripolyphosphate and mixed sodium and potassiumtripolyphosphate salts; and partially water-soluble or insolublebuilders such as crystalline layered silicates (EP-A-0164514 andEP-A-0293640) and aluminosilicates inclusive of Zeolites A, B, P, X, HSand MAP. The builder is typically present at a level of from about 1% toabout 80% by weight, preferably from about 10% to about 70% by weight,most preferably from about 20% to about 60% by weight of composition.

Amorphous sodium silicates having an SiO₂:Na₂O ratio of from 1.8 to 3.0,preferably from 1.8 to 2.4, most preferably 2.0 can also be used hereinalthough highly preferred from the viewpoint of long term storagestability are compositions containing less than about 22%, preferablyless than about 15% total (amorphous and crystalline) silicate.

Enzyme

Enzymes suitable herein include bacterial and fungal cellulases such asCarezyme and Celluzyme (Novo Nordisk A/S); peroxidases; lipases such asAmano-P (Amano Pharmaceutical Co.), M1 Lipase® and Lipomax®(Gist-Brocades) and Lipolase® and Lipolase Ultra® (Novo); cutinases;proteases such as Esperase®, Alcalase®, Durazym® and Savinase® (Novo)and Maxatase®, Maxacal®, Properase® and Maxapem® (Gist-Brocades); and αand β amylases such as Purafect Ox Am® (Genencor) and Termamyl®, Ban®,Fungamy®, Duramyl®, and Natalase® (Novo); and mixtures thereof. Enzymesare preferably added herein as prills, granulates, or cogranulates atlevels typically in the range from about 0.0001% to about 2% pure enzymeby weight of composition.

Bleaching Agent

Bleaching agents suitable herein include chlorine and oxygen bleaches,especially inorganic perhydrate salts such as sodium perborate mono-andtetrahydrates and sodium percarbonate optionally coated to providecontrolled rate of release (see, for example, GB-A-1466799 onsulfate/carbonate coatings), preformed organic peroxyacids and mixturesthereof with organic peroxyacid bleach precursors and/or transitionmetal-containing bleach catalysts (especially manganese or cobalt).Inorganic perhydrate salts are typically incorporated at levels in therange from about 1% to about 40% by weight, preferably from about 2% toabout 30% by weight and more preferably from abut 5% to about 25% byweight of composition. Peroxyacid bleach precursors preferred for useherein include precursors of perbenzoic acid and substituted perbenzoicacid; cationic peroxyacid precursors; peracetic acid precursors such asTAED, sodium acetoxybenzene sulfonate and pentaacetylglucose;pernonanoic acid precursors such as sodium3,5,5-trimethylhexanoyloxybenzene sulfonate (iso-NOBS) and sodiumnonanoyloxybenzene sulfonate (NOBS); amide substituted alkyl peroxyacidprecursors (EP-A-0170386); and benzoxazin peroxyacid precursors(EP-A-0332294 and EP-A-0482807). Bleach precursors are typicallyincorporated at levels in the range from about 0.5% to about 25%,preferably from about 1% to about 10% by weight of composition while thepreformed organic peroxyacids themselves are typically incorporated atlevels in the range from 0.5% to 25% by weight, more preferably from 1%to 10% by weight of composition. Bleach catalysts preferred for useherein include the manganese triazacyclononane and related complexes(U.S. Pat. No. 4,246,612, U.S. Pat. No. 5,227,084); Co, Cu, Mn and Febispyridylamine and related complexes (U.S. Pat. No. 5,114,611); andpentamine acetate cobalt(III) and related complexes(U.S. Pat. No.4,810,410).

Low Cloud Point Non-Ionic Surfactants and Suds Suppressers

The suds suppressers suitable for use herein include nonionicsurfactants having a low cloud point. “Cloud point”, as used herein, isa well known property of nonionic surfactants which is the result of thesurfactant becoming less soluble with increasing temperature, thetemperature at which the appearance of a second phase is observable isreferred to as the “cloud point” (See Kirk Othmer, pp. 360-362). As usedherein, a “low cloud point” nonionic surfactant is defined as a nonionicsurfactant system ingredient having a cloud point of less than 30° C.,preferably less than about 20° C., and even more preferably less thanabout 10° C., and most preferably less than about 7.5° C. Typical lowcloud point nonionic surfactants include nonionic alkoxylatedsurfactants, especially ethoxylates derived from primary alcohol, andpolyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO) reverseblock polymers. Also, such low cloud point nonionic surfactants include,for example, ethoxylated-propoxylated alcohol (e.g., Olin Corporation'sPoly-Tergent® SLF18) and epoxy-capped poly(oxyalkylated) alcohols (e.g.,Olin Corporation's Poly-Tergent® SLF18B series of nonionics, asdescribed, for example, in U.S. Pat. No. 5,576,281).

Preferred low cloud point surfactants are the ether-cappedpoly(oxyalkylated) suds suppresser having the formula:

wherein R¹ is a linear, alkyl hydrocarbon having an average of fromabout 7 to about 12 carbon atoms, R² is a linear, alkyl hydrocarbon ofabout 1 to about 4 carbon atoms, R³ is a linear, alkyl hydrocarbon ofabout 1 to about 4 carbon atoms, x is an integer of about 1 to about 6,y is an integer of about 4 to about 15, and z is an integer of about 4to about 25.

Other low cloud point nonionic surfactants are the ether-cappedpoly(oxyalkylated) having the formula:R_(I)O(R_(II)O)_(n)CH(CH₃)OR_(III)wherein, R_(I) is selected from the group consisting of linear orbranched, saturated or unsaturated, substituted or unsubstituted,aliphatic or aromatic hydrocarbon radicals having from about 7 to about12 carbon atoms; R_(II) may be the same or different, and isindependently selected from the group consisting of branched or linearC₂ to C₇ alkylene in any given molecule; n is a number from 1 to about30; and R_(III) is selected from the group consisting of:

-   -   (i) a 4 to 8 membered substituted, or unsubstituted heterocyclic        ring containing from 1 to 3 hetero atoms; and    -   (ii) linear or branched, saturated or unsaturated, substituted        or unsubstituted, cyclic or acyclic, aliphatic or aromatic        hydrocarbon radicals having from about 1 to about 30 carbon        atoms;    -   (b) provided that when R² is (ii) then either: (A) at least one        of R¹ is other than C₂ to C₃ alkylene; or (B) R² has from 6 to        30 carbon atoms, and with the further proviso that when R² has        from 8 to 18 carbon atoms, R is other than C₁ to C₅ alkyl.

Other suitable components herein include organic polymers havingdispersant, anti-redeposition, soil release or other detergencyproperties invention in levels of from about 0.1% to about 30%,preferably from about 0.5% to about 15%, most preferably from about 1%to about 10% by weight of composition. Preferred anti-redepositionpolymers herein include acrylic acid containing polymers such as SokalanPA30, PA20, PA15, PA10 and Sokalan CP10 (BASF GmbH), Acusol 45N, 480N,460N (Rohm and Haas), acrylic acid/maleic acid copolymers such asSokalan CP5 and acrylic/methacrylic copolymers. Preferred soil releasepolymers herein include alkyl and hydroxyalkyl celluloses (U.S. Pat. No.4,000,093), polyoxyethylenes, polyoxypropylenes and copolymers thereof,and nonionic and anionic polymers based on terephthalate esters ofethylene glycol, propylene glycol and mixtures thereof.

Heavy metal sequestrants and crystal growth inhibitors are suitable foruse herein in levels generally from about 0.005% to about 20%,preferably from about 0.1% to about 10%, more preferably from about0.25% to about 7.5% and most preferably from about 0.5% to about 5% byweight of composition, for example diethylenetriamine penta (methylenephosphonate), ethylenediamine tetra(methylene phosphonate)hexamethylenediamine tetra(methylene phosphonate), ethylenediphosphonate, hydroxy-ethylene-1,1-diphosphonate, nitrilotriacetate,ethylenediaminotetracetate, ethylenediamine-N,N′-disuccinate in theirsalt and free acid forms.

The compositions herein can contain a corrosion inhibitor such asorganic silver coating agents in levels of from about 0.05% to about10%, preferably from about 0.1% to about 5% by weight of composition(especially paraffins such as Winog 70 sold by Wintershall, Salzbergen,Germany), nitrogen-containing corrosion inhibitor compounds (for examplebenzotriazole and benzimadazole—see GB-A-1137741) and Mn(II) compounds,particularly Mn(II) salts of organic ligands in levels of from about0.005% to about 5%, preferably from about 0.01% to about 1%, morepreferably from about 0.02% to about 0.4% by weight of the composition.

Other suitable components herein include colorants, water-solublebismuth compounds such as bismuth acetate and bismuth citrate at levelsof from about 0.01% to about 5%, enzyme stabilizers such as calcium ion,boric acid, propylene glycol and chlorine bleach scavengers at levels offrom about 0.01% to about 6%, lime soap dispersants (see WO-A-93/08877),suds suppressors (see WO-93/08876 and EP-A-0705324), polymeric dyetransfer inhibiting agents, optical brighteners, perfumes, fillers andclay.

Liquid detergent compositions can contain low quantities of lowmolecular weight primary or secondary alcohols such as methanol,ethanol, propanol and isopropanol can be used in the liquid detergent ofthe present invention. Other suitable carrier solvents used in lowquantities includes glycerol, propylene glycol, ethylene glycol,1,2-propanediol, sorbitol and mixtures thereof.

EXAMPLES

Abbreviations Used in Examples

In the examples, the abbreviated component identifications have thefollowing meanings:

Carbonate: Anhydrous sodium carbonate STPP (anhydrous): Sodiumtripolyphosphate anhydrous STPP (hydrated): Sodium tripolyphosphatehydrated to approximately 8% Silicate: Amorphous Sodium Silicate(SiO₂:Na₂O = from 2:1 to 4:1) HEDP: Ethane 1-hydroxy-1,1-diphosphonicacid Perborate: Sodium perborate monohydrate Percarbonate: Sodiumpercarbonate of the nominal formula 2Na₂CO₃•3H₂O₂ Termamyl: α-amylaseavailable from Novo Nordisk A/S Savinase: protease available from NovoNordisk A/S FN3: protease available from Genencor SLF18: low foamingsurfactant available from Olin Corporation ACNI: alkyl capped non-ionicsurfactant of formula C_(9/11) H_(19/23) EO₈-cyclohexyl acetal C₁₄AO:tetradecyl dimethyl amine oxide C₁₆AO: hexadecyl dimethyl amine oxideDuramyl: α-amylase available from Novo Nordisk A/S DPG: dipropyleneglycol

In the following examples all levels are quoted as parts by weight.

Examples 1 to 4

The compositions of examples 1 to 4 are made in the form of a twocompartment PVA pouch. The dual compartment pouch is made from a MonosolM8630 film as supplied by Chris-Craft Industrial Products. The pouchesmade by presealing the liquid composition using the technique describedhereinabove. The particulate composition and the anhydrous compositionare placed in two different horizontal layered compartments, theanhydrous composition being placed above the particulate composition.The exemplified pouches show a good stability of the particulateautomatic dishwashing product.

Example 1 2 3 4 Particulate composition C₁₄ AO 5.55 5.55 C₁₆ AO 5.555.55 ACNI 5.55 5.55 SLF18 5.55 5.55 STPP (anhydrous) 21.0 21.0 21.0 21.0STPP (hydrated) 31.5 31.5 31.5 31.5 HEDP 1.0 1.0 1.0 1.0 Savinase 0.70.7 0.7 0.7 Termamyl 0.7 0.7 0.7 0.7 Perborate 13.55 13.55 Percarbonate13.55 13.55 Carbonate 15.0 10.0 15.0 15.0 Silicate 5.0 10.0 5.0 5.0Perfume 0.5 0.5 0.5 0.5 Anhydrous composition DPG 99.5 95.0 95.0 99.5FN3 Liquid 2.60 2.4 Duramyl Liquid 2.0 2.4 Dye 0.5 0.4 0.2 0.5

Examples 5 to 8

The particulate compositions of examples 1 to 4 are formed into tablets.The tablets are prepared as follows. The detergent composition isprepared by admixing the granular and liquid components and is thenpassed into the die of a conventional rotary press. The press includes apunch suitably shaped for forming a mould in the upper surface of thetablet. The cross-section of the die is approximately 30×38 mm. Thecomposition is then subjected to a compression force of 940 kg/cm², thepunch is elevated, and a tablet comprising the mould is ejected from thetablet press.

Separately, PVA pouches are formed and filled with the anhydrousauxiliary compositions of examples 1 to 4.

The multi-compartment pouches are made by placing PVA film into a trayhaving a series of tablet-shaped depressions. The tray is filled withtablets, the tablets being positioned into the tray such that the tabletmoulds are facing upwards. A layer of pouches comprising the anhydrouscomposition is placed with the pouches over and adjacent the moulds ofthe tablets and is used to close, by solvent sealing, the layer of openpouches comprising the tablets.

Monosol M8630 film as supplied by Chris-Craft Industrial Products wasused to make the pouches.

The exemplified pouches show a good stability of the particulateautomatic dishwashing product.

All documents cited in the Detailed Description of the Invention are, inrelevant part, incorporated herein by reference. A citation of anydocument is not to be construed as an admission that it is prior artwith respect to the present invention.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

1. A method of making a multi-compartment water soluble pouch comprisingthe steps of: (a) obtaining a first pouch material; (b) obtaining a moldhaving inner walls and a shape; (c) forming an open pouch in a mold fromthe first pouch material wherein the pouch material is flush with theinner walls of the mold, and takes the shape of the mold; and (d)closing said pouch by providing a second piece of pouch material andsealing said first pouch material and said second piece of pouchmaterial together, wherein said pouch is configured to define aninternal volume that is divided into two or more compartments, whereinpouch material creates a barrier that divides the internal volume ofsaid pouch into said two or more compartments which are separated fromeach other, and one of said compartments contains a particulate ordensified particulate automatic dishwashing product and another of saidcompartments contains an anhydrous liquid, gel or paste form of adishwashing detergent auxiliary wherein the compartment comprising thedetergent auxiliary is located above or adjacent the compartmentcomprising the particulate or densified particulate automaticdishwashing product.
 2. The method of claim 1 wherein the pouch is madeso that the compartment comprising the detergent auxiliary is locatedabove the compartment comprising the particulate or densifiedparticulate automatic dishwashing product.
 3. The method of claim 1wherein the pouch is made so that the compartment comprising thedetergent auxiliary is located adjacent the compartment comprising theparticulate or densified particulate automatic dishwashing product. 4.The method of claim 1 wherein said first pouch material and said secondpiece of pouch material comprise polyvinyl alcohol.